Stretch wrap films

ABSTRACT

The present invention provides for improved thermoplastic stretch wrap films having superior cling force, load retention, elongation, tear resistance and puncture resistance properties and for the methods of using those stretch wrap films. The stretch wrap films generally have a thickness of from about 0.4 to about 3 mils. The stretch wrap films are preferably constructed in a multilayer fashion having outside cling layers, and at least one inside puncture resistant layer comprising a metallocene-catalyzed polyethylene resin and at least one inside transverse direction tear resistant layer comprising a polyethylene copolymer.

FIELD OF THE INVENTION

The present invention is directed to stretch wrap films and methods for their use. In particular, the present invention is directed to stretch wrap films having superior puncture resistance, high elongation to break, high force to stretch the film, high cling force, and overall strength.

BACKGROUND OF THE INVENTION

The use of thermoplastic stretch wrap films for the overwrap packaging of goods, and in particular, the unitizing of palleted loads is a commercially significant application of polymer film, including generically, polyethylene. Overwrapping a plurality of articles to provide a unitized load can be achieved by a variety of techniques. In one procedure, the load to be wrapped is positioned upon a platform, or turntable, which is made to rotate and in so doing, to take up stretch wrap film supplied from a continuous roll. Braking tension is applied to the film roll so that the film is continuously subjected to a stretching, or tensioning, force as it wraps around the rotating load in overlapping layers. Generally, the stretch wrap film is supplied from a vertically arranged roll positioned adjacent to the rotating pallet load. Rotational speeds of from about 5 to 50 revolutions per minute are common. At the completion of the overwrap operation, the turntable is completely stopped and the film is cut and attached to an underlying layer of film employing tack sealing, adhesive tape, spray adhesives, etc. Depending upon the width of the stretch wrap roll, the load being overwrapped can be shrouded in the film while the vertically arranged film roll remains in a fixed position. Alternatively, the film roll, for example, in the case of relatively narrow film widths and relatively wide pallet loads, can be made to move in a vertical direction as the load is being overwrapped whereby a spiral wrapping effect is achieved on the packaged goods.

Another wrapping method finding acceptance in industry today is that of hand wrapping. In this method, the film is again arranged on a roll, however, it is hand held by the operator who walks around the goods to be wrapped, applying the film to the goods. The roll of film so used may be installed on a hand-held wrapping tool for ease of use by the operator.

Some of the properties desired of a good stretch wrap film are as follows: good cling or cohesion properties, high puncture resistance, high tear resistance in the transverse direction, good machine direction tear resistance, high stress retention, good transparency, low haze, low stress relaxation with time, high resistance to transverse tear when under machine direction tension, producible in thin gauges, low specific gravity and thus high yield in area per pound, good tensile toughness, high machine direction ultimate tensile strength, high machine direction ultimate elongation, and low modulus of elasticity.

Physical properties which are particularly significant for the successful use of thermoplastic films in stretch wrap applications include their puncture resistance, their elongation characteristics, their toughness and their resistance to tearing while under tension. In general, tensile toughness is measured as an area under a stress-strain curve developed for a thermoplastic film and it may be considered as the tensile energy absorbed, expressed in units of ft. lbs./cu.in. to elongate a film to break under tensile load. In turn, this toughness characteristic is a function of the capacity of such films to elongate. The process of stretching the film decreases that capacity. Accordingly, the stretch wrap process will decrease the toughness of the film while it is in its stretched condition as an overwrap as compared to its unstretched form. Generally this loss of toughness is proportional to the amount of stretch imparted to the film as it is overwrapping a load of goods.

Currently, different grades of stretch wrap films are commonly marketed for different end uses according to overall film properties. For example, certain stretch wrap films having superior properties for load retention are characterized by requiring a higher force to stretch the film. However, such load retention films generally have poor puncture characteristics at such stretch conditions. On the other hand, certain stretch wrap films having superior puncture resistance properties have low load retention properties, thus limiting their use.

A need exists to develop superior stretch wrap films characterized by having both superior load retention characteristics and puncture resistance characteristics. Such films could be used in a wider variety of end applications and thus not unduly limit users of stretch wrap films to selectively choosing a film based on its properties prior to initiating a stretch wrap application.

SUMMARY OF THE INVENTION

The present invention provides for superior cast stretch wrap films having improved cling, tear, elongation, and puncture resistance properties. The stretch wrap films can be used in cling/cling film applications. The stretch wrap film is advantageously employed in wrapping articles while under tension whereby the film itself is stretched generally to at least 200% of its original length.

The stretch wrap film of the present invention utilizes metallocene-catalyzed polyethylene resins in a unique way to take advantage of the improved puncture resistance properties of such resins. The metallocene-catalyzed polyethylene resins, however, are not desirable for use as stretch wrap film due to their poor cling performance, low transverse direction tear properties, and poor elongation to break performance. The films of the present invention are therefore constructed with various other film layers to remedy these deficiencies of the metallocene resins.

The stretch wrap film of the present invention is a multilayer film construction. In such a construction the two outside layers are cling layers, preferably constructed with a copolymer of ethylene and a minor amount of at least one alpha olefin of from about 3-12 carbon atoms whereby these outside film layers have a cling force to each other of at least about 140 g/inch. Between these two outside cling layers there is positioned at least one puncture resistant, inner polymeric film layer comprising at least 40 weight percent of a polyethylene copolymer having a polydispersity (M_(w) /M_(n) or MWD) of from 1 to 4, a melt index of from 0.5 to 10 g/10 min., and a melt flow ratio (I₂₀ /I₂) of from 12 to 22. The polyethylene copolymer used to construct the puncture resistant film layer is preferably produced utilizing metallocene catalyst polymerization techniques. At least one transverse direction tear resistant layer is located between the outside cling layers, wherein the resin comprising the tear resistant layer forms a film having a higher transverse direction tear resistance than films constructed with the resins that comprise the puncture resistant film layer and the outside cling layers.

The multilayer film can be constructed with additional film layers. For instance, additional puncture resistant film layers can be incorporated into the film between the outer cling layers, where such layers are constructed with the same or different metallocene-catalyzed polyethylene resins as the first puncture resistant film layer. A film can also be constructed with additional transverse direction tear resistant layers between the outer cling layers, again using the same or different resins for each distinct multiple layer.

The multilayer films of the present invention have been found to display unexpectedly superior film properties compared to other film constructions, surprisingly without undue degradation of other important film properties. The incorporation of an internal puncture resistant layer and an internal transverse direction tear resistant layer, using the resins for those layers as set forth herein, has produced an overall film that has superior elongation characteristics. Also, the films of the present invention display enhanced transverse direction tear properties without a concomitant loss of machine direction tear properties.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a four layer film constructed in accordance with the present invention.

FIG. 2 shows a five layer film constructed in accordance with the present invention.

FIG. 3 shows a five layer film constructed in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention sets forth multilayer stretch wrap thermoplastic films that are characterized by having a relatively high cling force, a relatively high puncture resistance, a relatively high force to elongate, and relatively high tear resistance in both the transverse and machine directions--a combination of properties not possessed by any previous chill roll cast stretch wrap film.

The multilayer stretch wrap films of the present invention are constructed with outer film cling layers. Between these outer layers the films are constructed with at least one layer of a polyethylene film possessing superior puncture resistance and at least one layer of a thermoplastic film possessing superior transverse direction tear properties. These multilayer stretch wrap films can be prepared as cast films by conventional coextrusion techniques.

The outside cling layers of the stretch wrap films of the present invention can be constructed of olefin polymer resins. Suitable polyethylene resins are those ethylenic copolymers that comprise a major proportion by weight of ethylene copolymerized with a minor proportion by weight of an alpha olefin monomer containing 3 to 12, preferably 4 to 10, and more preferably 4-8, carbon atoms. Preferred ethylenic copolymers are those commonly referred to as linear low density polyethylenes (LLDPE) and very low density polyethylenes (VLDPE), although the LLDPE resins are more preferred. Preferably the ethylenic copolymers employed are those having from about 1 to about 20, preferably from about 1 to about 10 weight percent of said higher alpha olefin monomer copolymerized therein. In addition, it is also preferred that the alpha olefin monomer employed in the ethylenic copolymer is selected from the group consisting of butene-1, 3-methyl-butene-1, 3-methylpentene-1, hexene-1, 4-methyl-pentene-1, 3-methyl-hexene-1, octene-1 and decene-1. Particularly preferred are the hexene-1 alpha olefins. The LLDPE resins are prepared at relatively low pressures employing coordination-type catalysts. Reference may be made to U.S. Pat. Nos. 3,645,992, 4,076,698, 4,011,382, 4,163,831, 4,205,021, 4,302,565, 4,302,566, 4,359,561 and 4,522,987 for more details of the manufacture and properties of LLDPE resins including those which are particularly useful herein.

The polyethylene resins that are desired to be used as the outside cling layers in films of the present invention are those that are functionally defined as providing a cling force of at least about 140, preferably at least about 180, more preferably at least about 220, and in some cases at least 260, grams/inch as determined by ASTM D 5458-94 test method. Generally, the cling force of the outside cling layers will be in the range of from about 140-300 grams/inch. Common LLDPE resins that can be used to form such an outside cling layer include those having a relatively high weight percentage of n-hexane extractibles, as measured by the n-hexane extractibles method of 21 C.F.R. 177.1520. Generally, the LLDPE used in the outside cling layers herein will contain from about 2 to about 10, preferably from about 2 to about 8, more preferably from about 2.5 to about 5, weight percent of n-hexane extractibles.

The LLDPE resins that can be used in the outside cling layers herein have a density ranging from about 0.890 to about 0.940 g/cm³, more commonly from about 0.90 to about 0.93 g/cm³, and a melt index of from about 1 to about 10 g/10 min. Particularly preferred are those LLDPE resins possessing densities within the range from about 0.917 to 0.920 g/cm³ and a melt index within the range from about 2.0 to 5.0 g/10 min. Examples of such LLDPE resins include those set forth in U.S. Pat. No. 5,273,809, which is hereby incorporated by reference in its entirety.

The polyethylene resins that are desired to be used as the outside cling layers in films of the present invention will have a polydispersity which is preferably in the range of from about 3 to about 4.

The VLDPE resins that can be used in the outside cling layers have a density ranging from about 0.880 to about 0.912 g/cm³, more commonly from about 0.89 to about 0.91 g/cm³, and a melt index of from about 0.5 to about 5, preferably from about 1 to about 3 g/10 min.

The LLDPE and VLDPE resins that can be used in the outside cling layers can be blended with minor amounts, e.g., up to about 40 weight percent total, of one or more other suitable resins to achieve a desired range of physical/mechanical properties in the film product. Thus, for example, such resins as ethyl vinyl acetate (EVA) copolymer, high pressure low density polyethylene (HPLDPE), and other LLDPE resins may be used for blending to obtain useful mixtures for forming the outside cling layers of the films of this invention.

The LLDPE and VLDPE resins that can be used in the outside cling layers herein can also contain known and conventional cling additives to augment the cling property that, at least in the case of the particularly preferred resins, is inherently exhibited. Examples of useful cling additives include poly-isobutylenes having a number average molecular weight in the range from about 1,000-3,000, preferably about 1,200-1,800, as measured by vapor phase osmometry, amorphous atactic polypropylenes, e.g., those having an average molecular weight of about 2000, and polyterpenes and ethylene-vinyl acetate copolymers containing from about 5-15 weight percent copolymerized vinyl acetate. The optional cling additive can be present in the outside cling layers in a concentration of from about 0.5 to about 10 weight percent of the resin. Of course, other conventional film additives such as antioxidants, UV stabilizers, pigments, dyes, etc., can be present in the usual amounts.

It is preferred to utilize the LLDPE resins that contain relatively high weight percentages of n-hexane extractibles for both of the outside cling layers due to overall performance results. However, one or both layers can be replaced by other known cling film layers such as a polymer film comprised from a first ethylene monomer and a second monomer that comprises an acrylate, where the acrylate content is from about 15-40% by weight of the polymer film, such as ethylene-acrylate (EA) polymer films, such as those shown in U.S. Pat. No. 5,049,423, which is incorporated herein in its entirety by reference. These EA polymers generally have an acrylate content between about 2-40%, preferably between about 10-35%, by weight based on the weight of the EA polymer. The acrylate useful in these polymers are those generally known in the art, preferably methyl, ethyl, and n-butyl acrylate.

The multilayer stretch wrap films of the present invention can be constructed to contain at least one inner film layer, located between the two outside cling layers, of a thermoplastic material possessing superior puncture resistance, and preferably good machine direction tear resistance. This puncture resistant film layer is made from a partially crystalline polyethylene resin, hereinafter "puncture resistant resin", that is a polymer prepared with ethylene and at least one alpha olefin monomer, e.g. a copolymer or terpolymer. The alpha olefin monomer generally has from 3 to about 12 carbon atoms, preferably from 4 to 10 carbon atoms, and more preferably from 6 to 8 carbon atoms. The alpha olefin comonomer content is generally below about 30 weight percent, preferably below about 20 weight percent, and more preferably from about 1 to about 15 weight percent. Exemplary comonomers include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. The puncture resistant resin generally has the characteristics associated with an LLDPE material, however it has improved properties as explained more fully below. The puncture resistant resin defined herein will have a density of from 0.88 to 0.94 g/cm³, preferably from 0.88 to 0.93 g/cm³, and more preferably from 0.88 to 0.925 g/cm³.

The weight average molecular weight of the puncture resistant resin can generally range from about 20,000 to about 500,000, preferably from about 50,000 to about 200,000. The molecular weight is determined by commonly used techniques such as size exclusion chromatography or gel permeation chromatography. The puncture resistant resin should have a molecular weight distribution, or polydispersity, (M_(w) /M_(n), "MWD") within the range of about 1 to about 4, preferably about 1.5 to about 4, more preferably about 2 to 4, and even more preferably from 2 to 3. The ratio of the third moment to the second moment, M_(z) /M_(w), is generally below 2.3, preferably below 2.0, and more typically in the range of from about 1.6-1.95. The melt flow ratio (MFR) of these resins, defined as I₂₀ /I₂ and as determined in accordance to ASTM D-1238, is generally from about 12 to about 22, preferably from about 14 to about 20, and more preferably from about 16 to about 18. The melt index (MI), defined as the I₂ value, should be in the range of from about 0.5 to about 10, preferably from about 1 to about 5 g/10 min.

Useful puncture resistant resin materials are available from, among others, Dow Chemical Company and Exxon Chemical Company who are producers of single site or constrained geometry catalyzed polyethylenes. These resins are commercially available as the AFFINITY and EXXACT polyethylenes (see Plastics World, p.33-36, January 1995), and also as the ENHANCED POLYETHYLENE and EXCEED line of resins. The manufacture of such polyethylenes, generally by way of employing a metallocene catalyst system, is set forth in, among others, U.S. Pat. Nos. 5,382,631, 5,380,810, 5,358,792, 5,206,075, 5,183,867, 5,124,418, 5,084,534, 5,079,205, 5,032,652, 5,026,798, 5,017,655, 5,006,500, 5,001,205, 4,937,301, 4,925,821, 4,871,523, 4,871,705, and 4,808,561, each of which is hereby incorporated herein by reference in its entirety. These catalyst systems and their use to prepare such puncture resistant resin materials are also set forth in EP 0 600 425 A1 and PCT applications WO 94/25271 and 94/26816. The polyethylene resins thus produced generally have a crystalline content in excess of at least 10 weight percent, generally in excess of at least 15 weight percent.

The above patents and publications generally report that these catalysts contain one or more cyclopentadienyl moieties in combination with a transition metal. The metallocene catalyst may be represented by the general formula C_(c) MA_(a) B_(b) wherein C is a substituted or unsubstituted cyclopentadienyl ring; M is a Group 3-10 metal or Lanthanide series element, generally a Group IVB, VB, or VIB metal; A and B are independently halogen, hydrocarbyl group, or hydrocarboxyl groups having 1-20 carbon atoms; a=0-3, b=0-3, and c=1-3. The reactions can take place in either gas phase, high pressure, slurry, or solution polymerization schemes.

The puncture resistant film layer of the present multilayer films is preferably constructed entirely with the puncture resistant resin, preferably produced through the metallocene catalyst technology. The puncture resistant film layer can also be constructed with a-blend of the puncture resistant resin with a second resin material. The second resin material is preferably a LLDPE resin having a density of between about 0.89 and 0.94 g/cm³, a LDPE resin having a density of between about 0.9 and 0.935 g/cm³, or VLDPE resin having a density of between about 0.88 and 0.91 g/cm³. The comonomer for the second resin material preferably has from 4-10, more preferably 6-8 carbon atoms. If a second resin material is to be incorporated with the puncture resistant resin, it is preferred to maintain the level of the puncture resistant resin to at least 40 weight percent, preferably at least 50 weight percent, and more preferably at least 60 weight percent, of the blended resin film. The resultant blended polymer resin maintains the desired properties of the puncture resistant resin material and may be more economical for certain applications.

The multilayer stretch wrap films of the present invention can contain at least one inner film layer, located between the two outside cling layers, of a thermoplastic material possessing superior transverse direction tear properties. The resin utilized in this film layer also contributes to the multilayer films of the present invention the ability to strain harden during the use of the film. The strain hardening characteristic can be generally described as the requirement to exert a higher force to continually stretch the film beyond its already stretched state. This film layer increases the machine direction tensile strength of the overall film.

Resins useful for preparing this transverse direction tear film layer include high pressure low density polyethylenes (HPLDPE) having a density within the range of from about 0.90 to about 0.935 g/cm³ with a melt index of from about 0.5 to about 10 g/10 min. A preferred HPLDPE resin is one having a density in the range of from about 0.915 to about 0.925 g/cm³, a melt index of from about 1 to about 10, preferably having a melt index from about 1 to about 5, and more preferably having a melt index of from 1 to 2.5 g/10 min. Other types of resins useful for preparing this film layer include polypropylene, generally isotatic polypropylene in a density range of 0.89-0.91 g/cm³ and a melt flow rate of from 5-25 g/10 min. as determined by ASTM D1238, ethylene-propylene copolymers having a density of between about 0.89 and 0.91 g/cm³ and a melt flow rate of from 2-10 g/10 min., and linear low density polyethylene resins having a density of between about 0.89 and 0.935 g/cm³ and having a melt index of below 2.0 g/10 min. The resin used for this tear resistant film layer preferably has a higher transverse direction tear resistance than the resins employed for the other film layers, e.g. the outside cling layers, and the puncture resistant film layer. That is, if separate films were prepared from each resin used for the individual film layers of the multilayer stretch films of the present invention, the resins used for the transverse direction tear resistant layer would produce a film having a higher transverse direction tear level than the films prepared from the resins used to prepare the outside layers and the puncture resistant layer.

The stretch wrap films of the present invention can be constructed to contain a plurality of layers of the tear resistant film and the puncture resistant film in various combinations. Generally, the stretch wrap film will be of an A\B\C\A construction as shown in FIG. 1 wherein the film layers (10) are the outside cling layers A, the film layer (20) is the puncture resistant film layer B, and the film layer (30) is the tear resistant film layer C.

In a preferred embodiment, the stretch wrap film is of an A\B\C\B\A or A\C\B\C\A construction such as those shown in FIGS. 2 and 3 where the film layers (10), (20), and (30) are the cling, puncture resistant, and tear resistant, layers, respectively, as previously described with respect to FIG. 1. Alternatively, film constructions such as A\B\B\C\A and A\B\C\C\A can also be prepared, and in addition films can be prepared having more than two layers of either the puncture resistant layers, layer B, and/or the tear resistant layer, layer C. In such constructions, the distinct B and C layers can be constructed with the same resins or with different resins to tailor the properties of the multilayer film.

The overall properties of the stretch wrap films of the present invention are such that it has a cling force of at least about 140, generally at least about 180, preferably at least about 200, more preferably at least about 220, and in some cases at least 260, grams/inch as determined by ASTM D5458-94. Generally, the cling force of the film will be in the range of from about 140-300 g/inch.

The overall stretch wrap films have relatively high puncture resistance, as measured by the F-50 dart drop test procedure (ASTM D1709). It is the experience of those skilled in the art that the F-50 dart drop test is well correlated to the end use puncture resistance of stretch wrap films. The F-50 dart drop value of the films is at least about 150 g/mil, preferably at least about 250 g/mil, and more preferably from at least about 350 g/mil. The multilayer films generally have an F-50 dart drop value below about 900 g/mil.

The stretch wrap films of the present invention are preferably constructed so that the overall transverse direction tear, as determined by ASTM D1922, is at least about 500 g/mil, preferably at least about 600 g/mil, more preferably at least about 700 g/mil. The machine direction tear of the film is generally at least about 175 g/mil, preferably at least about 225 g/mil, and more preferably at least about 275 g/mil.

A parameter used to analyze the performance of stretch wrap films is the force required to stretch the film to a desired percentage of its original length. This force is indicative of the load retention characteristics of the film and is determined in accordance with ASTM D882. The films of the present invention generally have a force to stretch the film to 200% of at least about 1600 psi, preferably at least about 1800 psi, more preferably at least about 2000 psi, and in some cases at least about 2200 psi. The films of the present invention generally have a force to stretch the film to 250% of at least about 1800 psi, preferably at least about 2000 psi, more preferably at least about 2250 psi, and in some cases at least about 2500 psi.

The films of the present invention generally have a gloss of at least about 88% and a haze of below about 2%.

The film configurations are constructed according to conventional practices. Generally, the preferred processing technique is to coextrude and cast the films in a simultaneous fashion, however in some cases it may be appropriate to first coextrude at least two film layers and thereafter extrusion coat the remaining film layers. It is preferred to employ known and conventional techniques of coextrusion to assemble the composite structures of the films of this invention. Reference may be made to U.S. Pat. No. 3,748,962, the contents of which are incorporated by reference herein, for details of a coextrusion procedure which can be employed in the fabrication of a multilayer film in accordance with this invention. Generally, the resin materials are heated to their molten state and their viscosities are coordinated to prepare multilayer films in a uniform manner. The molten materials are conveyed to a coextrusion adapter that combines the molten materials to form a multilayer coextruded structure. The layered polymeric material is transferred through an extrusion die opened to a predetermined gap commonly in the range of between about 0.05 in. (0.13 cm) and 0.012 in. (0.03 cm). The material is then drawn down to the intended gauge thickness by means of a primary chill or casting roll maintained at about 60°-130° F. (15°-55° C.). Typical draw down ratios range from about 5:1 to about 40:1.

The overall thickness of the stretch wrap film can vary widely according to end use specifications, but is generally in the range of the typical thicknesses for stretch wrap films. Conventional for such films is a thickness of from about 0.4 to about 3 mils, and is application specific.

In the present invention wherein the multilayer films are of a coextruded nature, it is preferred that the outer cling layers combined comprise from about 10 to about 50, preferably from about 10 to about 40, and more preferably from about 15 to about 30, weight percent of the total film weight. The transverse direction tear resistant film layer(s) comprise from about 2 to about 30, preferably from about 5 to about 20, and more preferably from about 5 to about 15, weight percent of the total film. The puncture resistant film layer(s) will account for the balance of the film, and generally will comprise from about 20 to about 85, preferably from about 40 to about 80, and more preferably from about 50 to about 75, weight percent of the film.

It has been found that the benefits provided from the transverse direction tear resistant film material are substantially obtained with up to about 15 weight percent, preferably up to about 10 weight percent, of the overall film. The incorporation of this film layer at these levels, in conjunction with the incorporation of the puncture resistant film layer, has led to an unexpected improvement in the machine direction tensile elongation, and machine direction stretch properties of the overall films. These properties have been found to be appreciably enhanced surprisingly without a significant loss of other important film properties, and as a result the overall film stretch wrap performance has been enhanced.

Either or both of the outside cling surfaces of the film can be treated by such known and conventional post-forming operations as corona discharge, chemical treatment, flame treatment, etc., to modify the printability or ink receptivity of the surface(s) or to impart other desirable characteristics thereto.

The stretch wrap film of this invention can, if desired, be provided in the non-stretched, i.e., unoriented, or at most only modestly stretched, state prior to use. The films of the present invention are capable of being stretched from at least about 10, more commonly at least about 100 or at least about 200, and in some cases at least about 300, linear percent during the overwrapping operation.

The pallet unitizing techniques described in U.S. Pat. Nos. 3,986,611 and 4,050,221 are contemplated herein. The disclosures of these patents are incorporated herein in their entirety by reference.

EXAMPLES

The following experiments were conducted to demonstrate various aspects of the multilayer films of the present invention.

The test procedures utilized in the following examples are set forth in the following Table.

    ______________________________________                                         STRETCH FILM TEST PROCEDURES                                                   TEST PROCEDURE    ASTM TEST METHOD                                             ______________________________________                                         Tensile Yield Machine                                                                            D882                                                         Direction (MD)                                                                 Tensile Ultimate MD                                                                              D882                                                         Tensile Elongation MD                                                                            D882                                                         Tensile Force @ 200% Stretch                                                                     D882                                                         250% Stretch      D882                                                         300% Stretch      D882                                                         350% Stretch      D882                                                         Elmendorf Tear MD D1922                                                        Elmendorf Tear Transverse                                                                        D1922                                                        Direction (TD)                                                                 Total Energy Dart Drop                                                                           D4272                                                        F-50 Dart Drop    D1709                                                        Gardner Gloss     D2457                                                        Gardner Haze      D1003                                                        Instron Peel Cling                                                                               D5458                                                        Instron Probe Puncture Energy                                                                    --                                                           ______________________________________                                    

The probe energy test was conducted by use of an Instron Universal tester that records a continuous reading of the force (stress) and penetration (strain) curve. A 6 in. by 6 in. film specimen is securely mounted to a compression load cell to expose a 4 in. by 4 in. area. A hemispherically shaped (1 in. dia.) stainless steel probe, traveling at a constant speed of 10 in./min is lowered into the film. A stress/strain curve is recorded and plotted. Peak force is the maximum force encountered. The machine is used to integrate the area under the curve, which is indicative of the energy consumed during the penetration to rupture testing of the film.

The films of the Examples were prepared using a pilot scale commercial cast film line machine. The material melt temperatures ranged from 480°-580° F. and were chosen to match melt viscosities of the various resins. The melts were conveyed to a coextrusion adapter that combines the melt flows into a multilayer coextruded structure. This layered flow was distributed through a single manifold film extrusion die to the required width. The die gap opening was nominally 0.025 inches. The material was drawn down to the final gauge. The material draw down ratio was about 31:1 for the 0.8 mil films. A vacuum box was used to pin the melt exiting the die opening to a primary chill roll maintained at about 90° F.

Example 1

The following example describes the properties of films prepared using a blend of a metallocene-catalyzed polyethylene (PE) resin with a linear low density polyethylene resin. These blends can be used to construct the puncture resistant film layer of the multilayer films of the present invention.

Various films were prepared from a resin blend containing a LLDPE resin, Resin A, and a metallocene-catalyzed PE resin, Resin B. The LLDPE resin, Resin A, was a resin having a density of 0.918 g/cm³, a 3.3 MI, a M_(n) of 22,000 and a M_(w) of 77,000. The metallocene-catalyzed PE resin, Resin B, was a hexene co-polymer polyethylene having a 3.3 MI, 0.918 g/cm³ density, a M_(n) of 26,000 and a M_(w) of 73,000. The resins were blended together and melted to form a homogeneous blend, and then extruded into a cast film having a thickness of about 0.8 mils. The film was then tested for various properties as set forth in Table 1.1.

The films were also tested for performance in a stretch wrapper constructed with equipment to determine various film properties during the stretching operation. The testing was conducted at rates similar to those employed by commercial equipment. The film width was 20 inches for this test machine. The machine direction (MD) force at 200% elongation, and maximum stretch and force values at breakage, were determined. The results are shown in Table

                                      TABLE 1.1                                    __________________________________________________________________________     TEST #       6      5     4     3     2     1                                  __________________________________________________________________________     SAMPLE DESCRIPTION                                                             Film Gauge (mils)                                                                           0.80   0.80  0.80  0.80  0.80  0.80                               Configuration                                                                               Single Layer B                                                                        Single Layer                                                                         Single Layer                                                                         Single Layer                                                                         Single Layer                                                                         Single Layer                                    Resin  AB Blends                                                                            AB Blends                                                                            AB Blends                                                                            AB Blends                                                                            A Resin                            Resin A, wt. %                                                                              0.0    20.0  40.0  60.0  80.0  100                                Resin B, wt. %                                                                              100.0  80.0  60.0  40.0  20.0  0.0                                LAB ANALYSIS                                                                   Tensile Ultimate MD                                                                         4663.0 5915.0                                                                               6216.0                                                                               5617.0                                                                               4801.0                                                                               4977.0                             (psi)                                                                          Tensile Elongation MD                                                                       520.0  585.0 656.0 638.0 603.0 603.0                              (%)                                                                            MD Force 200%                                                                               1615.0 1671.0                                                                               1465.0                                                                               1462.0                                                                               1463.0                                                                               1500.0                             Stretch (psi)                                                                  MD Force 250%                                                                               1734.0 1836.0                                                                               1527.0                                                                               1493.0                                                                               1519.0                                                                               1549.0                             Stretch (psi)                                                                  MD Force 300%                                                                               1969.0 2131.0                                                                               1692.0                                                                               1639.0                                                                               1573.0                                                                               1607.0                             Stretch (psi)                                                                  MD Force 350%                                                                               2334.0 2510.0                                                                               1935.0                                                                               1896.0                                                                               1852.0                                                                               1890.0                             Stretch (psi)                                                                  Elmendorf Tear MD                                                                           311.0  330.0 317.0 281.0 256.0 221.0                              (g/mil)                                                                        Elmendorf Tear TD                                                                           473.0  548.0 578.0 635.0 652.0 638.0                              (g/mil)                                                                        Instron Probe                                                                               19.5   18.2  18.3  22.9  21.9  25.1                               Puncture                                                                       Energy (in-lbs./mil)                                                           Total Energy Dart                                                                           58.9   57.4  29.5  22.5  15.6  19.0                               Drop                                                                           (in-lbs/mil)                                                                   F-50 Dart Drop                                                                              515+.sup.1                                                                            353.0 373.5 146.0 138.6 123.5                              (gms/mil)                                                                      Cling (grams/in)                                                                            72.8   118.9 152.2 191.5 207.6 220.5                              Gloss (%)    84.3   91.8  92.6  92.4  91.7  91.8                               Haze (%)     2.64   1.58  1.48  17.20 1.94  1.88                               STRETCH WRAP TESTER                                                            Force 200% Stretch                                                                          1.44   2.11  2.11  2.17  2.17  2.12                               (lb./in.)                                                                      Force Break (lb./in)                                                                        1.62   2.44  2.46  2.44  2.44  2.48                               Maximum Stretch to                                                                          334.0  375.0 385.0 380.0 382.0 401.0                              Break (%)                                                                      __________________________________________________________________________

The data in Table 1.1 show the benefit of using the metallocene-catalyzed PE resin to increase the puncture resistance of a film layer at high puncturing conditions.

For instance, the films having a majority of the metallocene-catalyzed PE resin had superior F-50 dart drop values. These films exhibited relatively low levels for cling, transverse direction tear, and tensile properties; these properties should be improved for the development of superior stretch wrap films.

It has been observed that the transverse directional tear of the films prepared with at least about 20 or 40 weight percent of the metallocene-catalyzed PE resin is catastrophic. That is, in the stretched condition, these films tear in the transverse direction in a clean, straight, and thoroughly instantaneous manner when a film defect is encountered such as a small hole, tear or puncture. This is in contrast to the tear exhibited by films that do not contain the metallocene-catalyzed PE resin, such as Film 1 in this example, which exhibits a highly distorted and rippled film tear indicating the absorption of energy during the tearing process. The catastrophic tear characteristic of the films containing the metallocene-catalyzed PE resin is an undesirable characteristic for a stretch wrap film. Such catastrophic tearing events will generally result in having to shut-down the automated stretch wrapping equipment with a significant economic loss.

Example 2

Experiments were conducted to compare the properties of a film having the metallocene-catalyzed polyethylene (PE) resin as a separate interior layer in a three layer film construction, ABA (A layers being cling layers), with certain of the single layer films of Example 1.

A three layer film, Film 7, was prepared having an ABA construction using the same metallocene-catalyzed PE resin used in Example 1 as the B core layer and a LLDPE resin having a density of 0.918 g/cm³, a MI of 3.3, a M_(n) of 18,000, and a M_(w) of 75,000 as the outer A layers. The two resins were coextruded with the overall A resin content set forth in Table 2.1, that content being essentially evenly split between both outside film layers.

Film 7 was then tested for various properties as set forth in Table 2.1, and compared to the properties obtained for Films 5 and 6 from Example 1. Film 5 was a single layer film made from a similar weight percent of metallocene-catalyzed PE resin (80%) to LLDPE resin (20%) as the multilayer Film 7, and Film 6 was a single layer film made with 100% of the metallocene-catalyzed PE resin.

Film 7 was also tested for performance in a stretch wrap tester as used in Example 1. The film width was 20 inches. The machine direction (MD) force at 200% elongation, and maximum stretch and force values at breakage, were determined. The results are shown in Table

                  TABLE 2.1                                                        ______________________________________                                         TEST #        5          6           7                                         ______________________________________                                         SAMPLE DESCRIPTION                                                             Film Gauge (mils)                                                                            0.80       0.80        0.80                                      Configuration Single Layer                                                                              Single Layer                                                                               A/B/A                                                   20% A/80% B                                                                               Metallocene (B)                                                                Resin                                                 Layer A, wt. %                                                                               --         --          20.0                                      Layer B, wt. %                                                                               --         --          80.0                                      LAB ANALYSIS                                                                   Tensile Ultimate MD (psi)                                                                    5915.0     4663.0      6984.0                                    Tensile Elongation MD                                                                        585.0      520.0       639.0                                     (%)                                                                            MD Force 200% 1671.0     1615.0      1586.0                                    Stretch (psi)                                                                  MD Force 250% Stretch                                                                        1836.0     1734.0      1689.0                                    (psi)                                                                          MD Force 300% Stretch                                                                        2131.0     1969.0      1887.0                                    (psi)                                                                          MD Force 350% Stretch                                                                        2510.0     2334.0      2156.0                                    (psi)                                                                          Elmendorf Tear MD                                                                            330.0      311.0       359.0                                     (g/mil)                                                                        Elmendorf Tear TD                                                                            548.0      473         542.0                                     (g/mil)                                                                        Instron Probe Puncture   19.5        20.5                                      Energy (in-lbs./mil)                                                                         18.2                                                             Total Energy Dart Drop   58.9        51.7                                      (in-lbs./mil) 57.4                                                             F-50 Dart Drop (g/mil)                                                                       353.0      515+        496.0                                     Cling (grams/in)                                                                             118.9      72.8        234.9                                     Gloss (%)     91.8       84.3        88.3                                      Haze (%)      1.58       2.64        2.06                                      STRETCH WRAP TESTER                                                            Force 200% Stretch                                                                           2.11       1.44        2.15                                      (lb./in.)                                                                      Force Break (lb./in.)                                                                        2.44       1.62        2.41                                      Maximum Stretch to                                                                           375.0      334.0       341.0                                     Break (%)                                                                      ______________________________________                                    

As can be seen from the results for Film 7, an ABA film construction with the metallocene-catalyzed PE resin as the core layer can be made having superior puncture resistance and superior cling properties. The ABA film construction of Film 7 displays superior cling properties compared to the metallocene-catalyzed PE film, Film 6, while maintaining superior puncture resistance properties as shown by the F-50 and total energy dart drop values. The 80/20 blend comparison for Film 7 to Film 5 from Example 1 shows that the separate interior layer of the metallocene-catalyzed PE resin used for Film 7 results in an increase in the overall F-50 dart drop value and improved cling properties for the overall film. The A/B/A construction of Film 7 thus displays superior properties for a stretch wrap film, however the elongation properties (as shown by the MD force stretch values and the maximum stretch to break on the stretch wrap tester) and transverse direction tear (Elmendorf TD tear) properties of the film can still be enhanced in accordance with the teachings of the present invention.

Example 3

Multilayer thermoplastic films were constructed in accordance with the teachings of the present invention as set forth in this example. These inventive films display unexpectedly superior film properties that result due to the incorporation of both a puncture resistant film layer and a transverse direction tear resistant layer as described herein.

Various experiments were conducted with a five layer film construction, ABCBA, where layers A were cling layers, layers B were puncture resistant layers, and layer C was a transverse direction tear resistant layer. The outer cling layers, layers A, were made from the LLDPE resin of Example 1. The inner core transverse direction tear resistant film layer, layer C, was made from a 2.0 MI LDPE resin having a density of 0.921 g/cm³. The inner core puncture resistant layer, layer B, was made from either the metallocene-catalyzed PE resin (MR) of Example 1 (Films 8-9) or a blend containing that metallocene-catalyzed PE resin with the LLDPE resin of Example 1 (Film 10). The five layer films were constructed with the weight percentages of the respective film layers as set forth in Table 3.1. The outside cling layers and the inside puncture resistant layers were generally equally weighted such that, for example, each of the outside cling layers constituted about 10% wt. of the overall film. The films were all nominally 0.8 mil thick. The results of the testing of the various films are set forth in Table 3.1.

The films were also tested for performance in a stretch wrap tester as in Example 1. The film width was 20 inches. The machine direction (MD) force at 200% elongation, and maximum stretch and force values at breakage, were determined. The results are shown in Table 3.1.

The test results for Film 7 from Example 2 are also shown in Table 3.1 for comparison.

                                      TABLE 3.1                                    __________________________________________________________________________     TEST #         7      8      9      10                                         __________________________________________________________________________     SAMPLE DESCRIPTION                                                             Film Gauge (mils)                                                                             0.80   0.80   0.80   0.80                                       Configuration  A/B/A  A/B/C/B/A                                                                             A/B/C/B/A                                                                             A/B/C/B/A                                  Resin Component Layer A                                                                       3.3 MI LLDPE                                                                          3.3 MI LLDPE                                                                          3.3 MI LLDPE                                                                          3.3 MI LLDPE                               Layer A, wt. % 20.0   20.0   20.0   20.0                                       Resin Component Layer B                                                                       3.3 MI MR                                                                             3.3 MI MR                                                                             3.3 MI MR                                                                             60% 3.3 MI MR                                             LLDPE  LLDPE  LLDPE  LLDPE/                                                                         40% 3.3 MI                                                                     LLDPE                                      Layer B, wt. % 80.0   70.0   60.0   60.0                                       Resin Component Layer C                                                                       --     2.0 MI LDPE                                                                           2.0 MI LDPE                                                                           2.0 MI LDPE                                Layer C, wt. % --     10.0   20.0   20.0                                       LAB ANALYSIS                                                                   Tensile Ultimate MD (psi)                                                                     6984.0 6031.0 5212.0 3419.0                                     Tensile Elongation MD (%)                                                                     639.0  627.0  595.0  443.0                                      MD Force 200% Stretch (psi)                                                                   1586.0 1856.0 2116.0 2231.0                                     MD Force 250% Stretch (psi)                                                                   1689.0 1962.0 2255.0 2361.0                                     MD Force 300% Stretch (psi)                                                                   1887.0 2167.0 2451.0 2542.0                                     MD Force 350% Stretch (psi)                                                                   2156.0 2432.0 2715.0 2771.0                                     Elmendorf Tear MD (g/mil)                                                                     359.0  373.0  281.0  244.0                                      Elmendorf Tear TD (g/mil)                                                                     542.0  633.0  659.0  615.0                                      Instron Probe Puncture                                                                        20.5   18.1   15.9   17.3                                       Energy (in-lbs/mil)                                                            Total Energy Dart Drop                                                                        51.7   39.9   21.8   14.1                                       (in-lbs/mil)                                                                   F-50 Dart Drop (g/mil) (grams/in.)                                                            496.0  474.5  162.5  140.0                                      Cling (grams/in.)                                                                             234.9  257.8  276.6  243.3                                      Gloss (%)      88.3   88.4   88.6   88.8                                       Haze (%)       2.06   2.05   1.84   1.70                                       STRETCH WRAP TESTER                                                            Force 200% Stretch (lb./in.)                                                                  2.15   2.47   2.97   2.88                                       Force Break (lb./in)                                                                          2.41   2.86   3.18   3.26                                       Maximum Stretch to Break (%)                                                                  341.0  395.0  388.0  392.0                                      __________________________________________________________________________

The inventive films, Films 8-10, display the beneficial properties of films prepared in accordance with the present invention. The films have high cling performance and high MD and TD tear resistances. The puncture resistance of the films is superior, particularly for those films containing below about 20% wt. of the LDPE resin as the C layer.

It was also found that the elongation performance of the inventive films was unexpectedly improved due to the incorporation of both the puncture resistant layer, layer B, and the transverse direction tear resistant layer, layer C. This is shown by the improved test results for the MD force tests at 200-350% stretch and the maximum stretch to break test on the stretch wrap tester.

It was further found that the transverse tear characteristics of the inventive films was not of a catastrophic nature, but was more of a feathered nature, in distinction to those films containing the metallocene-catalyzed PE resin in Example 1. The preparation of films that do not exhibit catastrophic transverse direction tear failure is an important aspect to the construction of a stretch wrap film as the film will not be subject to catastrophic tear failure in use if a puncture should occur.

These examples show that the inventive multilayer films provide an overall film possessing superior cling, puncture, elongation, and transverse tear resistance properties, while maintaining high levels of machine direction tear resistance. 

What is claimed is:
 1. A method for stretch wrapping an item, comprising wrapping the item with a multilayer, thermoplastic stretch wrap film containing at least four polymeric film layers, said film comprising:(a) a first outer polymeric cling film layer; (b) a second outer polymeric cling film layer, said first and said second outer cling film layers having a cling force to each other of at least about 140 grams/inch as determined by ASTM D5458-94; (c) a puncture resistant, inner polymeric film layer, located between said first and second outer layers, said puncture resistant layer comprising at least 40 weight percent of a polyethylene copolymer or terpolymer resin, said polyethylene resin having a polydispersity of from 1 to 4, a melt index of from 0.5 to 10 g/10 min., and a melt flow ratio (I₂₀ /I₂) of from 12 to 22; and (d) a tear resistant, inner polymeric film layer, located between said first outer layer and said puncture resistant inner layer, said tear resistant layer constructed with a resin that produces a film having a higher transverse direction tear resistance than a film produced by the resins used to construct said puncture resistant film layer and said first and second outer film layers; wherein said stretch wrap film has a transverse direction tear resistance of at least 500 g/mil, a machine direction tear resistance of at least about 175 g/mil, and a F-50 dart drop value of at least 150 g/mil as determined by ASTM D1709; and whereby said multilayer, thermoplastic film is stretched during the wrapping step.
 2. The method of claim 1 wherein said first and second outer film layers have a cling force to each other of at least about 180 grams/inch.
 3. The method of claim 1 wherein said polyethylene resin of said puncture resistant layer has a density of from about 0.88 to about 0.94 g/cm³.
 4. The method of claim 1 wherein said polyethylene resin of said puncture resistant layer comprises at least about 50 weight percent of said puncture resistant film layer.
 5. The method of claim 4 wherein the F-50 dart drop value of said stretch wrap film is at least about 250 g/mil.
 6. The method of claim 4 wherein the stretch wrap film has a force required to elongate the film 200% of at least 1800 psi and a force required to elongate the film 250% of at least 2000 psi.
 7. The method of claim 6 having a force required to elongate the film 200% of at least 2000 psi and a force required to elongate the film 250% of at least 2250 psi.
 8. The method of claim 4 wherein the stretch wrap film has a transverse direction tear resistance of at least 600 g/mil.
 9. The method claim 8 having a transverse direction tear resistance of at least 700 g/mil.
 10. The method of claim 4 wherein the stretch wrap film is constructed such that said outer layers comprise from about 10 to about 30 weight percent of said film, said tear resistant film layer comprises from about 5 to about 15 weight percent of said film, and said puncture resistant film layer comprises from about 40 to about 85 weight percent of said film.
 11. The method of claim 4 wherein the resin used to construct the tear resistant film layer of the stretch wrap film comprises a low density polyethylene resin having a density in the range of from about 0.90 to about 0.935 with a melt index of from about 0.5 to about 10 g/10 min.
 12. The method of claim 1 wherein said polyethylene resin of said puncture resistant film layer is made using a metallocene catalyst.
 13. The method of claim 1 further comprising a cling additive.
 14. The method of claim 13 wherein said cling additive is poly-isobutylene.
 15. A method for stretch wrapping an item, comprising:wrapping the item with a multilayer, thermoplastic stretch wrap film containing at least four polymeric film layers, said film comprising: (a) a first outer polymeric film layer comprising a polymer of two or more monomers, wherein a first monomer is ethylene, in a major amount by weight, and a second monomer is an alpha olefin of from about 3-12 carbon atoms, in a minor amount by weight; (b) a second outer polymeric film layer comprising a polymer of two or more monomers, wherein a first monomer is ethylene, in a major amount by weight, and a second monomer is an alpha olefin of from about 3-12 carbon atoms, in a minor amount by weight, said first and said second outer film layers having a cling force to each other of at least about 140 grams/inch as determined by ASTM D5458-94; (c) a puncture resistant, inner polymeric film layer, located between said first and second outer layers, said puncture resistant layer comprising at least 40 weight percent of a polyethylene copolymer or terpolymer resin, said polyethylene resin having a polydispersity of from 1 to 4, a melt index of from 0.5 to 10 g/10 min., and a melt flow ratio (I₂₀ /I₂) of from 12 to 22; and (d) a tear resistant, inner polymeric film layer, located between said first outer layer and said puncture resistant inner layer, said tear resistant layer constructed with a resin that produces a film having a higher transverse direction tear resistance than a film produced by the resins used to construct said puncture resistant film layer and said first and second outer film layers; wherein said stretch wrap film has a transverse direction tear resistance of at least 500 g/mil, a machine direction tear resistance of at least about 175 g/mil, and a F-50 dart drop value of at least 150 g/mil as determined by ASTM D1709.
 16. The method of claim 15 wherein said polyethylene resin of said puncture resistant film layer has a density of from 0.88 to 0.94 g/cm³.
 17. The method of claim 15 wherein said resin of said puncture resistant film layer comprises at least about 50 weight percent of said puncture resistant film layer.
 18. The method of claim 17 wherein said polyethylene resin of said puncture resistant film layer has a polydispersity of 2 to
 4. 19. The method of claim 17 wherein said film has a machine direction tear resistance of at least 225 g/mil.
 20. The method of claim 17 wherein the F-50 dart drop value of said stretch wrap film is at least about 250 g/mil.
 21. The method of claim 20 wherein said film has a force required to elongate the film 200% of at least 1800 psi and a force required to elongate the film 250% of at least 2000 psi.
 22. The method of claim 21 having a force required to elongate the film 200% of at least 2000 psi and a force required to elongate the film 250% of at least 2250 psi.
 23. The method of claim 15 wherein said film has a transverse direction tear resistance of at least 600 g/mil.
 24. The method of claim 23 having a transverse direction tear resistance of at least 700 g/mil.
 25. The method of claim 20 wherein said outer layers comprise from about 10 to about 40 weight percent of said film, said tear resistant film layer comprises from about 5 to about 20 weight percent of said film, and said puncture resistant film layer comprises from about 20 to about 80 weight percent of said film.
 26. The method of claim 20 wherein said outer layers comprise from about 10 to about 30 weight percent of said film, said tear resistant film layer comprises from about 5 to about 15 weight percent of said film, and said puncture resistant film layer comprises from about 40 to about 85 weight percent of said film.
 27. The method of claim 17 wherein said stretch wrap film further comprises at least one additional puncture resistant, inner polymeric film layer, located between said first and said second outer layers, said additional puncture resistant layer comprising at least 40 weight percent of a polyethylene resin, said polyethylene resin having a polydispersity of from 1 to 4, a melt index of from 0.5 to 10 g/10 min., and a I₂₀ /I₂ melt flow ratio of from 14 to
 20. 28. The method of claim 17 wherein said stretch wrap film further comprises at least one additional tear resistant, inner polymeric film layer, located between said first and second outer layers, said additional tear resistant layer constructed with a resin that produces a film having a higher transverse direction tear resistance than a film produced by the resins used to construct said puncture resistant film layer and said first and second outer film layers.
 29. The method of claim 15 wherein said polyethylene resin of said puncture resistant film layer is made using a metallocene catalyst.
 30. The method of claim 15 further comprising a cling additive.
 31. The method of claim 30 wherein said cling additive is poly-isobutylene.
 32. A method for stretch wrapping an item, comprising:wrapping the item with a multilayer, thermoplastic stretch wrap film containing at least four polymeric film layers, said film comprising: (a) a first outer polymeric film layer comprising a linear low density polyethylene resin having a density from about 0.89 to about 0.94 g/cm³ and having a melt index of from 1 to 10 g/10 min., said resin containing from about 2 to about 8 weight percent n-hexane extractibles; (b) a second outer polymeric film layer comprising a linear low density polyethylene resin having a density from about 0.89 to about 0.94 g/cm³ and having a melt index of from 1 to 10 g/10 min., said resin containing from about 2 to about 8 weight percent n-hexane extractibles; said first and said second outer film layers having a cling force to each other of at least about 140 grams/inch as determined by ASTM D5458-94; (c) a puncture resistant, inner polymeric film layer, located between said first and second outer layers, said puncture resistant layer comprising at least 40 weight percent of a polyethylene copolymer or terpolymer resin, said polyethylene resin having a polydispersity of from 1 to 4, a melt index of from 0.5 to 10 g/10 min., and a melt flow ratio (I₂₀ /I₂) of from 12 to 22; and (d) a tear resistant, inner polymeric film layer, located between said first outer layer and said puncture resistant inner layer, said tear resistant layer comprising a high pressure low density polyethylene resin having a density of from about 0.90 to about 0.935 g/cm³ and a melt index of from about 0.5 to about 10 g/10 min.; wherein said stretch wrap film has a transverse direction tear resistance of at least 500 g/mil, a machine direction tear resistance of at least about 175 g/mil, and a F-50 dart drop value of at least 150 g/mil. as determined by ASTM D1709.
 33. The method of claim 32 wherein said polyethylene resin of said puncture resistant film layer has a density of from 0.88 to 0.94 g/cm³.
 34. The method of claim 32 wherein said resin of said puncture resistant film layer comprises at least about 50 weight percent of said puncture resistant film layer.
 35. The method of claim 32 wherein said polyethylene resin of said puncture resistant film layer has a polydispersity of 2 to
 4. 36. The method of claim 32 wherein said stretch wrap film has a machine direction tear resistance of at least 225 g/mil.
 37. The method of claim 32 wherein the F-50 dart drop value of said stretch wrap film is at least about 250 g/mil.
 38. The method of claim 32 wherein said stretch wrap film has a force required to elongate the film 200% of at least 1800 psi and a force required to elongate the film 250% of at least 2000 psi.
 39. The method of claim 38 having a force required to elongate the film 200% of at least 2000 psi and a force required to elongate the film 250% of at least 2250 psi.
 40. The method of claim 32 wherein said stretch wrap film has a transverse direction tear resistance of at least 600 g/mil.
 41. The method of claim 32 having a transverse direction tear resistance of at least 700 g/mil.
 42. The method of claim 32 wherein said outer layers comprise from about 10 to about 30 weight percent of said film, said tear resistant film layer comprises from about 5 to about 15 weight percent of said film, and said puncture resistant film layer comprises from about 40 to about 85 weight percent of said film.
 43. The method of claim 32 wherein said polyethylene resin of said puncture resistant film layer is made using a metallocene catalyst.
 44. The method of claim 32 further comprising a cling additive.
 45. The method of claim 44 wherein said cling additive is poly-isobutylene.
 46. A method for stretch wrapping an item, comprising wrapping the item with a multilayer, thermoplastic stretch wrap film containing at least four polymeric film layers, said film comprising:(a) a first outer polymeric film layer comprising a copolymer of ethylene and an alpha olefin of 6-8 carbon atoms, in a minor amount by weight, said copolymer having a polydispersity of from about 3 to about 4, a density from about 0.9 to about 0.93 g/cm³, a melt flow ratio (I₂₀ /1₂) of from 22-32; and a melt index of from 2 to 5 g/10 min.; (b) a second outer polymeric film layer comprising a copolymer of ethylene and an alpha olefin of 6-8 carbon atoms, in a minor amount by weight, said copolymer having a polydispersity of from about 3 to about 4, a density from about 0.9 to about 0.93 g/cm³, a melt flow ratio (I₂₀ /I₂) of from 22-32; and a melt index of from 2 to 5 g/10 min., said first and said second outer film layers having a cling force to each other of at least about 180 grams/inch as determined by ASTM D5458-94; (c) a puncture resistant, inner polymeric film layer, located between said first and second outer layers, said puncture resistant layer comprising at least 40 weight percent of a copolymer of ethylene and hexene prepared using a metallocene catalyst, said copolymer having a polydispersity of from 2 to 3, a melt index of from 1 to 5 g/10 min., and a melt flow ratio (I₂₀ /I₂) of from 16 to 18; and (d) a tear resistant, inner polymeric film layer, located between said first outer layer and said puncture resistant inner layer, said tear resistant layer constructed with a resin that produces a film having a higher transverse direction tear resistance than a film produced by the resins used to construct said puncture resistant film layer and said first and second outer film layers; wherein said stretch wrap film has a transverse direction tear resistance of at least 700 g/mil, a machine direction tear resistance of at least about 225 g/mil, and a F-50 dart drop value of at least 250 g/mil as determined by ASTM D1709 and has a force required to elongate the film 200% of at least 2000 psi and a force required to elongate the film 250% of at least 2250 psi; and whereby said multilayer, thermoplastic film is stretched during the wrapping step.
 47. A method for stretch wrapping an item, comprising wrapping the item with a multilayer, thermoplastic stretch wrap film containing at least four polymeric film layers, including a first and a second outer polymeric film layer, wherein said first and said second outer film layers have a cling force to each other of at least about 140 grams/inch and wherein said stretch wrap film has a transverse direction tear resistance of at least 500 g/mil, a machine direction tear resistance of at least about 175 g/mil, and a F-50 dart drop value of at least about 150 g/mil as determined by ASTM D1709.
 48. The method of claim 47 wherein said first and said second outer film layers have a cling force to each other of at least about 180 grams/inch.
 49. The method of claim 47 wherein said film has a machine direction tear resistance of at least 225 g/mil.
 50. The method of claim 47 wherein the F-50 dart drop value of said stretch wrap film is at least about 250 g/mil.
 51. The method of claim 47 having a force required to elongate the film 200% of at least 1800 psi and a force required to elongate the film 250% of at least 2000 psi.
 52. The method of claim 51 having a force required to elongate the film 200% of at least 2000 psi and a force required to elongate the film 250% of at least 2250 psi.
 53. The method of claim 47 having a transverse direction tear resistance of at least 600 g/mil.
 54. The method of claim 53 having a transverse direction tear resistance of at least 700 g/mil. 